State Theory Research Articles

Holding on until the barrel is empty? Algeria's bumpy trajectory towards a post-rentier state

Rentier states are under increasing pressure to move towards a post-rentier state model as peak oil demand is approaching. However, it remains unclear if or how a rentier state can make this transition. To answer this, I developed an analytical framework including the mechanisms from the rentier state theory that need to be present to move towards a post-rentier state. This analytical framework is hypothetical, as up to now, no rentier state has been able to transition to a post-rentier state. Using Algeria as a case study, this novel framework is used to analyse the incremental evolution Algeria has made towards a post-rentier state since the year 2000. I argue that Algeria experienced several internal as well as external opportunities and threats and was influenced by its history on how it responded. Although Algeria fulfilled several steps of the framework, it failed to fulfil necessary sustainability aspects to become a post-rentier state.

Impact of Temperature on Reaction Rate in Catalytic Reactions

Purpose: The aim of the study was to assess the impact of temperature on reaction rate in catalytic reactions. Methodology: This study adopted a desk methodology. A desk study research design is commonly known as secondary data collection. This is basically collecting data from existing resources preferably because of its low cost advantage as compared to a field research. Our current study looked into already published studies and reports as the data was easily accessed through online journals and libraries. Findings: The study indicated that as higher temperatures generally increase the rate at which reactions occur. This is due to the fact that elevated temperatures provide the reactant molecules with more kinetic energy, enabling them to collide more frequently and with greater force, which is necessary to overcome the activation energy barrier. In catalytic reactions, temperature not only accelerates the intrinsic rate of the reaction but can also affect the activity and selectivity of the catalyst. However, too high a temperature can lead to catalyst deactivation through processes such as sintering or coke formation, where the catalyst surface is altered or blocked. Thus, an optimal temperature range is crucial to balance enhanced reaction rates while maintaining catalyst integrity and performance. Implications to Theory, Practice and Policy: Arrhenius equation, transition state theory and collision theory may be used to anchor future studies on the impact of temperature on reaction rate in catalytic reactions. In practical applications, industries should implement advanced temperature control systems to maintain optimal reaction conditions during catalytic processes. Policymakers have a critical role in shaping the landscape of catalytic reactions by developing regulatory guidelines focused on temperature management.

Analysis of differential scanning calorimetry data for aged plutonium.

Differential scanning calorimetry data for samples of a 52 year old plutonium alloy with 3.3 at. % Ga that were heated beyond the melting point is analyzed using transition state theory to find activation energies for the δ to ɛ and ɛ to liquid phase transitions. A Bayesian statistical method involving a Gaussian process model is used to find mean values and confidence intervals for the activation energies. The activation energy for the δ to ɛ phase transition increases by 3.3 ± 3.8% per decade, relative to the case when all age related plutonium lattice point defects have been removed through annealing. The corresponding increase in activation energy for the ɛ to liquid transition is shown to be 7.1 ± 1.8% per decade. It is postulated that the change in activation energy with age for both phase transitions is caused, in part, by the accumulation of the same type of lattice point defects associated with the observed increase in elastic bulk modulus over time.

The characteristics and mechanism of NaHCO3 compound fly ash in suppressing gas explosions in pipeline networks

Gas has been widely concerned due to its importance in the industrial and energy fields. In order to improve the inhibition effect of gas explosion, under the self-constructed pipe network system, the inhibition of gas explosion by composite inhibitor of fly ash and NaHCO3 with different ratios was investigated, and the microscopic inhibition mechanism of the two kinds of powders on the explosion of gas was investigated based on the method of density functional theory and transition state theory from the perspective of molecular dynamics. The results show that: the composite powder explosion suppression is better than a single powder, explosion suppression effect with the increase in the proportion of the mass of NaHCO3 significantly improve the 5 groups of conditions NaHCO3 loading of 40% (by mass) is the best, this time, the explosion of the peak overpressure, the peak flame propagation velocity, the peak flame temperature compared to the maximum reduction in the percentage of the measures taken for the maximum of 74.42%, 81.93%, 68.71%. In addition, NaHCO3, fly ash effectively inhibit the key primitive reaction of gas explosion. When the temperature reaches a certain point, the two and O*, O2, OH* and H* reaction rate higher than the rate of CH4 oxidation chain reaction, the dominant reaction, the maximum difference in rate constants of 70.95, 58.81, 60.06, 44.94. The study of the transition from the macro-scale to the molecular level of the study, in-depth understanding of the mechanism of explosion suppression, to reduce the risk of explosion from the ground up, and enriches the Gas explosion prevention and control of the theoretical system, for the operators to provide a strong technical guarantee for safe production.

Multiple status signals in multinational teams: Implications of lingua franca proficiency and task expertise for informal leadership

Lingua franca proficiency and task expertise coexist in multinational teams as prominent status signals that are often relied upon to infer a member’s competence. These personal attributes, however, do not always suggest consistent information since those with lower lingua franca proficiency might be more expert at the task and vice versa. In examining their joint implications, we draw on status characteristics and expectation states theories to identify the signaling nature of each attribute. Unlike the categorically specific quality of task expertise, lingua franca proficiency possesses characteristics commensurate with both specific and diffuse signals: it represents a social group and, at the same time, carries valid information about performance for certain tasks. Using archival (Study 1) and experimental (Study 2) data, we explore how the hybrid nature of lingua franca proficiency shapes its interaction with task expertise and implications for subsequent leadership outcomes. We provide further evidence for the generalizability of our findings through a supplemental study that includes 18 interviews with current members of multinational teams across various organizations.

Low-dimensional projection of reactivity classes in chemical reaction dynamics using supervised dimensionality reduction.

Transition state theory (TST) provides a framework to estimate the rate of chemical reactions. Despite its great success with many reaction systems, the underlying assumptions such as local equilibrium and nonrecrossing do not necessarily hold in all cases. Although dynamical systems theory can provide the mathematical foundation of reaction tubes existing in phase space that enables us to predict the fate of reactions free from the assumptions of TST, numerical demonstrations for large systems have been yet one of the challenges. Here, we propose a dimensionality reduction algorithm to demonstrate structures in phase space (called reactive islands) that predict reactivity in systems with many degrees of freedom. The core of this method is the application of supervised principal component analysis, where a coordinate transformation is performed to preserve the dynamical information on reactivity (i.e., to which potential basin the system moves from a region of interest) as much as possible. The reactive island structures are expected to be reflected in the transformed, low-dimensional phase space. As an illustrative example, the algorithm is scrutinized using a modified Hénon-Heiles Hamiltonian system extended to many degrees of freedom, which has three channels leading to three different products from one stable potential basin. It is shown that our algorithm can predict the reactivity in the transformed, low-dimensional coordinate system better than a naïve coordinate system and that the reactivity distribution in the transformed low-dimensional space is considered to reflect the underlying reactive islands.

The effects of toxin and mutual interference among zooplankton on a diffusive plankton–fish model with Crowley–Martin functional response

A diffusive phytoplankton–zooplankton–fish model with toxin and Crowley–Martin functional response is considered. By the global bifurcation theorem and the fixed point index theory, the existence and multiplicity of coexistence states are discussed. Secondly, we investigate the bifurcation from a double eigenvalue by virtue of Lyapunov–Schmidt procedure and implicit function theorem. Then, the effect of large k, which measures the magnitude of interference among zooplankton, is studied by means of the combination of the perturbation theory and topological degree theory. The results indicate that if k is large enough, this system has only a unique asymptotically stable coexistence state provided that toxin is properly small and the maximal growth rates of phytoplankton and fish are suitably large. Furthermore, the extinction and permanence of the time-dependent system are determined by virtue of the comparison principle. Finally, we make some numerical simulations to validate and complement the theoretical analysis and exhibit the critical role of toxin, spatial diffusion and magnitude of interference among zooplankton in the dynamics. The findings suggest that the spatiotemporal dynamics of the systems with toxin and Crowley–Martin functional response are richer and more complex, and toxin and spatial diffusion have significant effects on the coexistence of phytoplankton–zooplankton–fish species.

Understanding right-wing populists’ anti-abortion politics in Turkey: The symbolic violence of the state

This study investigates how symbolic violence is shaping anti-abortion stances associated with legitimising right-wing populist policies. The prominent questions are as follows: What are the institutional and politico-administrative mechanisms that are impacting anti-abortion politics in terms of material and symbolic violence? How and to what extent does anti-abortion politics influence the interplay between symbolic and material state violence? The study argues that reproduction-centred policies and material and symbolic violence have intensified through anti-abortion politics in the discursive context of the social reproduction crisis in Turkey. It explores the institutional actions and the legitimation mechanisms of anti-abortion policies in relation to the penetration of right-wing populist politics after the authoritarian turn of 2010. This qualitative case study uses critical discourse analysis. It interprets the public speeches of representatives of the government and documentary data concerning the ruling party’s programmes, development plans and relevant legislation. The research provides a gendered perspective on the anti-abortion policies that anchor right-wing populism in terms of the crisis of social reproduction. It also contributes to critical state theory and pre-existing feminist scholarship on right-wing populism.

Synthesis of spiro[oxindole-2,3′-pyrrolidine] derivatives via exo-selective 1,3-dipolar cycloaddition reaction, characterization and DFT investigation

A series of spiro[oxindole-2,3′-pyrrolidine] derivatives (4a-q) were successfully synthesized via an exo-selective 1,3-dipolar cycloaddition reaction between a stabilized azomethine ylide and various (E)-3-arylidene-1-methylpyrrolidine-2,5-diones. The structures and stereochemistry of the cycloadducts were elucidated through 1D and 2D NMR spectroscopic techniques. The preferred reaction pathway was corroborated by DFT calculations using the B3LYP functional with the 6–31 G (d, p) basis set. The results revealed that the cycloaddition reaction follows a normal electron demand mechanism, where the azomethine ylide acts as the nucleophile and the dipolarophile as the electrophile. The Fukui function analysis favors the regio 2, contradicting the experimental observations while, transition state theory aligns perfectly with the experimental results.

How to simulate dissociative chemisorption of methane on metal surfaces.

The dissociation of methane is not only an important reaction step in catalytic processes, but also of fundamental interest. Dynamical effects during the dissociative chemisorption of methane on metal surfaces cause significant differences in computed reaction rates, compared to what is predicted by typical transition state theory (TST) models. It is clear that for a good understanding of the catalytic activation of methane dynamical simulations are required. In this paper, a general blueprint is provided for performing dynamical simulations of the dissociative chemisorption of methane on metal surfaces, by employing either the quasi-classical trajectory or ring polymer molecular dynamics approach. If the computational setup is constructed with great care-since results can be affected considerably by the setup - chemically accurate predictions are achievable. Although this paper concerns methane dissociation, the provided blueprint is, so far, applicable to the dissociative chemisorption of most molecules.

Atmospheric Chemistry of Chloroprene Initiated by OH Radicals: Combined Ab Initio/DFT Calculations and Kinetics Analysis.

Chloroprene (CP; CH2═C(Cl)-CH═CH2) is a significant toxic airborne pollutant, often originating from anthropogenic activities. However, the environmental fate of CP is incompletely understood. High level CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ calculations combined with kinetic modeling were employed here to glean new insight into the reaction mechanism, energies, and kinetics of the reaction of CP with OH radical (•OH). We report the energies of four different addition pathways and six different abstraction pathways. The •OH attack on the terminal C1 atom of the =CH2 group (which is directly attached to the =CCl moiety), leading to the formation of HOCH2-•C(Cl)-CH═CH2, was found to be a major path. The barrier height for the formation of the corresponding transition state was found to be -1.9 kcal mol-1 below that of the starting CP + •OH reactants. Rate coefficients were calculated for addition and abstraction pathways involving the CP + •OH reaction under pre-equilibrium approximation conditions, employing a combination of canonical variational transition state theory and small curvature tunneling. The overall rate coefficient for the reaction of CP + •OH at 298 K was found to be 1.4 × 10-10 cm3 molecule-1 s-1. The thermochemistry of the possible channels and atmospheric implications are provided. In addition, the fate of HOCH2-•C(Cl)-CH═CH2 in the presence of 3O2 was investigated. We found the reaction of the CP-derived peroxy radical adduct with HO2 and NO to make contributions to the formation of products such as formaldehyde, HO2 radical, Cl atom, HOCH2C(OOH)(Cl)CH═CH2, HOCH2C(O)Cl, ClC(O)CH═CH2, HOCH2C(O)CH═CH2, and HC(O) radical.

Literature Review on Thermodynamic and Kinetic Limitations of Thermal Decomposition of Methane

The state of the art in methane pyrolysis does not yet provide a definitive answer as to whether the concept of an elementary reaction is universally applicable to the apparently simple process of methane dissociation. Similarly, the literature currently lacks a comprehensive and unambiguous description of the methane pyrolysis process and, in particular, a single model that would well represent its course at both the micro and macro scales. Given the wide range of conditions under which this reaction can occur—whether thermal or thermo-catalytic, in solid or fluidized bed reactors—it is crucial to evaluate the usefulness of different kinetic models and their compatibility with basic thermodynamic principles and design assumptions. To address these research gaps, the authors analysed the thermodynamic and kinetic dependencies involved in the thermal decomposition of methane, using the synthesis of methane from its elemental components and its reversibility as a basis for exploring suitable kinetic models. Using experimental data available in the literature, a wide range of kinetic models have been analysed to determine how they all relate to the reaction rate constant. It was found that regardless of whether the process is catalytic or purely thermal, for temperatures above 900 °C the reversibility of the reaction has a negligible effect on the hydrogen yield. This work shows how the determined kinetic parameters are consistent with the Kinetic Compensation Effect (KCE) and, by incorporating elements of Transition State Theory (TST), the possibility of the existence of Entropy–Enthalpy Compensation (EEC). The indicated correspondence between KCE and EEC is strengthened by the calculated average activation entropy at isokinetic temperature (∆SB=−275.0 J·(mol·K)−1). Based on these results, the authors also show that changes in the activation energy (E=20–421 kJ·mol−1) can only serve as an estimate of the optimal process conditions, since the isoconversion temperature (Tiso=1200−1450 K>Teq) is shown to depend not only on thermodynamic principles but also on the way the reaction is carried out, with temperature (T) and pressure (P) locally compensating each other.

The Local Welfare State and Differences in Racialized Poverty

ABSTRACT Researchers concerned with the U.S. welfare state have documented that more localized administration allows for greater geographic variation in public policies as well as the greater potential for racial discrimination to influence policy outcomes. I explore whether key attributes of the local welfare state, capacity and spending, are associated with differences in racialized poverty across localities. I develop a conceptual framework drawing on two sociological traditions: spatial inequality framework and local welfare state theory. Spatial inequality scholarship provides a framework for interrogating why poverty varies across localities and racialized groups. Local welfare scholarship conceptualizes the processes by which local governments impact poverty and how those processes may be highly racialized. Drawing on data from the Census of Governments, I examine all local governments’ capacity and spending across counties in the U.S. and their association with poverty rates among white, Black, and Hispanic populations. I find that local governments’ capacity and spending do matter to understanding differences in racialized poverty. Specifically, racialized groups perceived as more deserving are likely to be the beneficiaries of local government interventions and policies. This study calls for greater attention to the local welfare state as a possible mechanism maintaining racial stratification.

Unimolecular isomerizations of C6H6•+ radical cations: a computational study.

Eighteen concerted isomerization reactions of various C6H6•+ radical cation (RC) species are studied and found to proceed via well-defined transition states, whose relative positions along the reaction pathway generally agree with Hammond's postulate. From the barrier heights, the rate coefficients of these reactions are estimated by using transition state theory, and the activation energies are computed. Through combination among themselves, these 18 isomerizations yielded 15 multi-step conversion routes of various C6H6•+ species to the lowest energy benzene radical cation isomer 1, which routes are compared. Use is made of DFT with the B3LYP and M06-2X functionals, along with the CBS-QB3 approach to arrive at better energies. From the barrier heights for each of the concerted reactions, canonical transition state theory was applied to evaluate rate coefficients k over the temperature range 200-500K. The Arrhenius activation energies were computed using the plot of ln k vs. 1/T.

A Strategy for Modeling Nonstatistical Reactivity Effects: Combining Chemical Activation Estimates with a Vibrational Relaxation Model.

The kinetics of many chemical reactions can be readily explained with a statistical approach, for example, using a form of transition state theory and comparing calculated Gibbs energies along the reaction coordinate(s). However, there are cases where this approach fails, notably when the vibrational relaxation of the molecule to its statistical equilibrium occurs on the same time scale as the reaction dynamics, whether it is caused by slow relaxation, a fast reaction, or both. These nonstatistical phenomena are then often explored computationally using (quasi)classical ab initio molecular dynamics by calculating a large number of trajectories while being prone to issues such as zero-point energy leakage. On the other side of the field, we see resource-intensive quantum dynamics simulations, which significantly limit the size of explorable systems. We find that using a Fermi's golden rule type of model for vibrational relaxation, based on anharmonic coupling constants, we can extract the same qualitative information while giving insights into how to enhance (or destroy) the bottlenecks causing the phenomena. We present this model as a middle ground for exploring complex nonstatistical behavior, capable of treating medium-sized organic molecules or biologically relevant fragments. We also cover the challenges involved, in particular quantifying the excess energy in terms of vibrational modes. Relying on readily available electronic structure methods and providing results in a simple master equation form, this model shows promise as a screening tool for opportunities in mode-selective chemistry without external control.

Georg Friedrich Knapp's Legacy to Modern Monetary Theory: A Reconsideration

This article is a reassessment of the relation between Georg Friedrich Knapp and Modern Monetary Theory, a contemporary strand of economics that, under the term chartalism coined by Knapp, is presented by its proponents as a continuation of his 1905 State Theory of Money. It shows that, contrary to Modern Monetary Theory, which proposes a policy-oriented monetary view of public deficit, Knapp's scientific aim is restricted to finding a generally valid concept of means of payments. Different meanings of the terms chartalism and money also separate the two theories. However, both share an understanding of the use of money as driven by taxes and a general concept of means of payment as a situational counterclaim over a central issuer, be it private or public. In their view, private money always holds subordinate rank inside public monetary systems because of imposed convertibility into state currency. Despite such theoretical convergence, the article shows that Knapp's chartalist theory was not rediscovered from oblivion in the mid-1990s when Modern Monetary Theory made its appearance, in which it arguably played no decisive role.

The Big Bang versus the Steady State: Gamow, Hoyle and Ryle, rivals in cosmology

Abstract This account of the controversy concerning the Big Bang and Steady State theories contrasts the different approaches to science of George Gamow, Fred Hoyle and Martin Ryle. Einstein’s general relativity offered theoretical physicists an indispensable tool kit for making mathematical models of the Universe. Georges Lemaître made an astonishing impact in 1927 with his proposal that the expanding Universe started from a decaying super-radioactive primeval atom. Gamow refined Lemaître’s model by proposing that primordial nucleosynthesis in the early expanding Universe had formed the chemical elements. Hoyle, who by contrast had discovered the conditions under which stellar nucleosynthesis could occur via the evolution and explosion of massive stars, publicly dismissed Gamow’s cosmology as an unnecessary speculation. Hoyle, Hermann Bondi and Thomas Gold proposed the alternative steady state theory in 1948. In 1950 Ryle constructed the first radio telescope with the sensitivity to discriminate between the rival models of the Universe. Steady state cosmology survived Ryle’s first surveys of cosmic radio sources because Ryle’s data was inadequate. However results from the much improved Third and Fourth Cambridge Surveys demonstrated that our Universe had evolved. The Ryle-Hoyle debates became intensely passionate and personal. In 1965 the discovery of the cosmic microwave background radiation settled the argument in favour of the Lemaître Big Bang evolving Universe.

First-principles study on the mechanism of Hf and Ti doping promoting hydrogen release in ZrCoH3

This paper reveals the mechanism of Hf and Ti doping promoting hydrogen release in ZrCoH3. Different from previous experimental methods, this study employs the plane wave pseudopotential method and density functional theory to predict the relationship between the formation energy and electronic structure of the ZrCoH3-Hf/Ti system, and uses theoretical calculations to guide the modification design of ZrCoH3. Firstly, by calculating the thermodynamic properties of the ZrCoH3-Hf/Ti system and combining the density of states theory, the bonding characteristics and dehydrogenation preference between H atoms and neighboring metal atoms in the ZrCoH3-Hf/Ti system are determined. Additionally, the electronic structure of the ZrCoH3-Hf/Ti system is calculated to elucidate the hybridization of bonding and antibonding orbitals between atoms in the ZrCoH3-Hf/Ti system. Moreover, DCo-d is utilized to measure the strength of antibonding interactions in the ZrCoH3-Hf/Ti system. The main cause of antibonding interactions in the ZrCoH3-Hf/Ti system is attributed to the variation in formation energy, and the change in antibonding interactions is sensitive to the variation in formation energy. Finally, a feasible method to improve the properties of ZrCoH3 is proposed, which involves modifying the electronic structure to increase the partial density of states at the Fermi energy level, making the formation energy of hydrides less negative and forcing the structure to be more unstable. This method has potential application value in the modification of ZrCoH3.

Boosting lithium/magnesium separation performance of selective electrodialysis membranes regulated by enamine reaction

Monovalent cation exchange membranes (MCEMs) have progressively played an important role in the field of ion separation. However, according to transition state theory (TST), synchronously tuning the enthalpy barrier (△H) and entropy barrier (△S) for cation transport to improve ion separation performance is challenging. Here, the enamine reaction between the -NH- and -CHO groups is applied to regulate the subsequent Schiff-base reaction between the -CHO and -NH2 groups, which reduces the positive charges of the selective layer but increases the steric hindrance. The increased -T△S (△S term) for cation transport plays an important role in improving Li+/Mg2+ separation performance. The optimal positively-charged glutaraldehyde@piperazine/polyethyleneimine assembled membrane (M-Glu@PIP/PEI) has a perm-selectivity (Li+/Mg2+) of 31.83 with a Li+ flux of 1.87 mol·m-2·h-1, surpassing the Li+/Mg2+ separation performance of state-of-the-art monovalent ion selective membranes (MISMs). Most importantly, the selective electrodialysis (S-ED) process with M-Glu@PIP/PEI can be directly applied to treat simulated salt-lake brines (SLBs), and its superior Li+/Mg2+ separation performance and operational stability enables 74.44% of the lithium resources with a Li+ purity of 34.02% to be recovered. This study presents new insights into the design of high-performance MCEMs for energy-efficient resource recovery.

The Effect of the Surrounding Matrix on Spin Transition Nanoparticles: How Shell Characteristics Alter Core Elastic Properties in Core‐Shell Particles

A surrounding matrix is known to alter nanoparticle spin transitions, the solid state structural phase changes associated with transitions between high spin (HS) and low spin(LS) states. To better quantify how the spin transition solid and surrounding matrix interact, several series of core‐shell particles were prepared based on RbxCo[Fe(CN)6]z∙nH2O, RbCoFe‐PBA, as spin transition core with isostructural shells of different compositions and thicknesses. Synchrotron PXRD through the thermal high HS to LS, the LS to photoexcited high spin (PXHS), and thermal PXHS to LS transitions, show the activation energy is lowered as shells become thicker and stiffer. Calorimetry data coupled with transition state theory analysis indicate the core stiffens in the core‐shell particles relative to the uncoated particles. The conclusion is supported by microstrain analysis that shows stiffer shells limit the extent to which the core distorts as individual sites transition, leading to the lower activation energy. Finally, differences in lattice mismatch with different shell materials are shown to alter the mechanism by which the transition progresses.